CN103959152A - Method for manufacturing liquid crystal alignment film, liquid crystal alignment film, and liquid crystal display element - Google Patents
Method for manufacturing liquid crystal alignment film, liquid crystal alignment film, and liquid crystal display element Download PDFInfo
- Publication number
- CN103959152A CN103959152A CN201280058353.6A CN201280058353A CN103959152A CN 103959152 A CN103959152 A CN 103959152A CN 201280058353 A CN201280058353 A CN 201280058353A CN 103959152 A CN103959152 A CN 103959152A
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- China
- Prior art keywords
- liquid crystal
- side chain
- chain type
- polymeric membrane
- type polymeric
- Prior art date
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- Granted
Links
- 239000004973 liquid crystal related substance Substances 0.000 title claims abstract description 299
- 238000000034 method Methods 0.000 title claims abstract description 130
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 85
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- 230000010287 polarization Effects 0.000 claims abstract description 41
- 238000010438 heat treatment Methods 0.000 claims abstract description 40
- 238000002835 absorbance Methods 0.000 claims abstract description 18
- 230000001678 irradiating effect Effects 0.000 claims abstract description 18
- 239000012528 membrane Substances 0.000 claims description 198
- 238000006243 chemical reaction Methods 0.000 claims description 45
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 17
- 125000000217 alkyl group Chemical group 0.000 claims description 16
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 15
- 229910052799 carbon Inorganic materials 0.000 claims description 15
- 125000004093 cyano group Chemical group *C#N 0.000 claims description 13
- 125000005843 halogen group Chemical group 0.000 claims description 13
- 125000003545 alkoxy group Chemical group 0.000 claims description 12
- 229920002521 macromolecule Polymers 0.000 claims description 12
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 10
- WBYWAXJHAXSJNI-VOTSOKGWSA-M .beta-Phenylacrylic acid Natural products [O-]C(=O)\C=C\C1=CC=CC=C1 WBYWAXJHAXSJNI-VOTSOKGWSA-M 0.000 claims description 9
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 claims description 9
- GRZJZRHVJAXMRR-UHFFFAOYSA-N 1-cyclohexyl-2-phenylbenzene Chemical group C1CCCCC1C1=CC=CC=C1C1=CC=CC=C1 GRZJZRHVJAXMRR-UHFFFAOYSA-N 0.000 claims description 8
- 150000002790 naphthalenes Chemical class 0.000 claims description 8
- DMLAVOWQYNRWNQ-UHFFFAOYSA-N azobenzene Chemical compound C1=CC=CC=C1N=NC1=CC=CC=C1 DMLAVOWQYNRWNQ-UHFFFAOYSA-N 0.000 claims description 6
- 230000033228 biological regulation Effects 0.000 claims description 6
- 125000000753 cycloalkyl group Chemical group 0.000 claims description 6
- 150000002240 furans Chemical class 0.000 claims description 6
- WBYWAXJHAXSJNI-UHFFFAOYSA-N methyl p-hydroxycinnamate Natural products OC(=O)C=CC1=CC=CC=C1 WBYWAXJHAXSJNI-UHFFFAOYSA-N 0.000 claims description 6
- 125000000168 pyrrolyl group Chemical group 0.000 claims description 6
- 229930016911 cinnamic acid Natural products 0.000 claims description 5
- 235000013985 cinnamic acid Nutrition 0.000 claims description 5
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims description 4
- DQFBYFPFKXHELB-UHFFFAOYSA-N Chalcone Natural products C=1C=CC=CC=1C(=O)C=CC1=CC=CC=C1 DQFBYFPFKXHELB-UHFFFAOYSA-N 0.000 claims description 4
- WBYWAXJHAXSJNI-SREVYHEPSA-N Cinnamic acid Chemical compound OC(=O)\C=C/C1=CC=CC=C1 WBYWAXJHAXSJNI-SREVYHEPSA-N 0.000 claims description 4
- PQMOXTJVIYEOQL-UHFFFAOYSA-N Cumarin Natural products CC(C)=CCC1=C(O)C(C(=O)C(C)CC)=C(O)C2=C1OC(=O)C=C2CCC PQMOXTJVIYEOQL-UHFFFAOYSA-N 0.000 claims description 4
- FSOGIJPGPZWNGO-UHFFFAOYSA-N Meomammein Natural products CCC(C)C(=O)C1=C(O)C(CC=C(C)C)=C(O)C2=C1OC(=O)C=C2CCC FSOGIJPGPZWNGO-UHFFFAOYSA-N 0.000 claims description 4
- JRXXLCKWQFKACW-UHFFFAOYSA-N biphenylacetylene Chemical compound C1=CC=CC=C1C#CC1=CC=CC=C1 JRXXLCKWQFKACW-UHFFFAOYSA-N 0.000 claims description 4
- 235000005513 chalcones Nutrition 0.000 claims description 4
- 229940114081 cinnamate Drugs 0.000 claims description 4
- ZYGHJZDHTFUPRJ-UHFFFAOYSA-N coumarin Chemical compound C1=CC=C2OC(=O)C=CC2=C1 ZYGHJZDHTFUPRJ-UHFFFAOYSA-N 0.000 claims description 4
- DQFBYFPFKXHELB-VAWYXSNFSA-N trans-chalcone Chemical compound C=1C=CC=CC=1C(=O)\C=C\C1=CC=CC=C1 DQFBYFPFKXHELB-VAWYXSNFSA-N 0.000 claims description 4
- 239000004215 Carbon black (E152) Substances 0.000 claims description 3
- 229930195733 hydrocarbon Natural products 0.000 claims description 3
- 150000002430 hydrocarbons Chemical group 0.000 claims description 3
- FCJSHPDYVMKCHI-UHFFFAOYSA-N phenyl benzoate Chemical compound C=1C=CC=CC=1C(=O)OC1=CC=CC=C1 FCJSHPDYVMKCHI-UHFFFAOYSA-N 0.000 claims description 3
- PJANXHGTPQOBST-VAWYXSNFSA-N Stilbene Natural products C=1C=CC=CC=1/C=C/C1=CC=CC=C1 PJANXHGTPQOBST-VAWYXSNFSA-N 0.000 claims description 2
- PJANXHGTPQOBST-UHFFFAOYSA-N stilbene Chemical compound C=1C=CC=CC=1C=CC1=CC=CC=C1 PJANXHGTPQOBST-UHFFFAOYSA-N 0.000 claims description 2
- 235000021286 stilbenes Nutrition 0.000 claims description 2
- 229920006254 polymer film Polymers 0.000 abstract 4
- 239000005266 side chain polymer Substances 0.000 abstract 4
- 230000001747 exhibiting effect Effects 0.000 abstract 1
- 210000004379 membrane Anatomy 0.000 description 185
- 238000004132 cross linking Methods 0.000 description 23
- 230000015572 biosynthetic process Effects 0.000 description 22
- 239000000126 substance Substances 0.000 description 21
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- 230000000052 comparative effect Effects 0.000 description 20
- 238000003786 synthesis reaction Methods 0.000 description 20
- 230000008707 rearrangement Effects 0.000 description 18
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 16
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 15
- 230000005855 radiation Effects 0.000 description 15
- 239000000203 mixture Substances 0.000 description 14
- 238000001338 self-assembly Methods 0.000 description 14
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- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 9
- 229910052760 oxygen Inorganic materials 0.000 description 9
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- 238000007699 photoisomerization reaction Methods 0.000 description 8
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 8
- HOSGXJWQVBHGLT-UHFFFAOYSA-N 6-hydroxy-3,4-dihydro-1h-quinolin-2-one Chemical group N1C(=O)CCC2=CC(O)=CC=C21 HOSGXJWQVBHGLT-UHFFFAOYSA-N 0.000 description 6
- 229920001721 polyimide Polymers 0.000 description 6
- 150000001875 compounds Chemical class 0.000 description 5
- 238000006471 dimerization reaction Methods 0.000 description 5
- 239000003999 initiator Substances 0.000 description 5
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- 230000003321 amplification Effects 0.000 description 4
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 4
- 238000011156 evaluation Methods 0.000 description 4
- 238000003199 nucleic acid amplification method Methods 0.000 description 4
- NAWXUBYGYWOOIX-SFHVURJKSA-N (2s)-2-[[4-[2-(2,4-diaminoquinazolin-6-yl)ethyl]benzoyl]amino]-4-methylidenepentanedioic acid Chemical compound C1=CC2=NC(N)=NC(N)=C2C=C1CCC1=CC=C(C(=O)N[C@@H](CC(=C)C(O)=O)C(O)=O)C=C1 NAWXUBYGYWOOIX-SFHVURJKSA-N 0.000 description 3
- 238000000576 coating method Methods 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- XXMIOPMDWAUFGU-UHFFFAOYSA-N hexane-1,6-diol Chemical compound OCCCCCCO XXMIOPMDWAUFGU-UHFFFAOYSA-N 0.000 description 3
- 238000005286 illumination Methods 0.000 description 3
- 238000006317 isomerization reaction Methods 0.000 description 3
- 238000005457 optimization Methods 0.000 description 3
- YJTKZCDBKVTVBY-UHFFFAOYSA-N 1,3-Diphenylbenzene Chemical group C1=CC=CC=C1C1=CC=CC(C=2C=CC=CC=2)=C1 YJTKZCDBKVTVBY-UHFFFAOYSA-N 0.000 description 2
- XQISPVJWRLHHLT-UHFFFAOYSA-N 1-hydroxycyclohexa-2,4-diene-1-carboxylic acid Chemical compound OC(=O)C1(O)CC=CC=C1 XQISPVJWRLHHLT-UHFFFAOYSA-N 0.000 description 2
- VSMDINRNYYEDRN-UHFFFAOYSA-N 4-iodophenol Chemical compound OC1=CC=C(I)C=C1 VSMDINRNYYEDRN-UHFFFAOYSA-N 0.000 description 2
- 239000005711 Benzoic acid Substances 0.000 description 2
- UEXCJVNBTNXOEH-UHFFFAOYSA-N Ethynylbenzene Chemical compound C#CC1=CC=CC=C1 UEXCJVNBTNXOEH-UHFFFAOYSA-N 0.000 description 2
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 2
- 239000004372 Polyvinyl alcohol Substances 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 210000002469 basement membrane Anatomy 0.000 description 2
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- 239000004305 biphenyl Substances 0.000 description 2
- 230000015556 catabolic process Effects 0.000 description 2
- OMFXVFTZEKFJBZ-HJTSIMOOSA-N corticosterone Chemical compound O=C1CC[C@]2(C)[C@H]3[C@@H](O)C[C@](C)([C@H](CC4)C(=O)CO)[C@@H]4[C@@H]3CCC2=C1 OMFXVFTZEKFJBZ-HJTSIMOOSA-N 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 2
- 239000000428 dust Substances 0.000 description 2
- 239000004744 fabric Substances 0.000 description 2
- VHRYZQNGTZXDNX-UHFFFAOYSA-N methacryloyl chloride Chemical compound CC(=C)C(Cl)=O VHRYZQNGTZXDNX-UHFFFAOYSA-N 0.000 description 2
- 229920002451 polyvinyl alcohol Polymers 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 238000007639 printing Methods 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 238000004528 spin coating Methods 0.000 description 2
- 230000006641 stabilisation Effects 0.000 description 2
- 238000011105 stabilization Methods 0.000 description 2
- 230000003068 static effect Effects 0.000 description 2
- FYSNRJHAOHDILO-UHFFFAOYSA-N thionyl chloride Chemical compound ClS(Cl)=O FYSNRJHAOHDILO-UHFFFAOYSA-N 0.000 description 2
- SGRHVVLXEBNBDV-UHFFFAOYSA-N 1,6-dibromohexane Chemical compound BrCCCCCCBr SGRHVVLXEBNBDV-UHFFFAOYSA-N 0.000 description 1
- CFDRQRFAQCJPBZ-UHFFFAOYSA-N 1-chlorohexan-1-ol Chemical compound CCCCCC(O)Cl CFDRQRFAQCJPBZ-UHFFFAOYSA-N 0.000 description 1
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
- XKZQKPRCPNGNFR-UHFFFAOYSA-N 2-(3-hydroxyphenyl)phenol Chemical compound OC1=CC=CC(C=2C(=CC=CC=2)O)=C1 XKZQKPRCPNGNFR-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- ONIKNECPXCLUHT-UHFFFAOYSA-N 2-chlorobenzoyl chloride Chemical compound ClC(=O)C1=CC=CC=C1Cl ONIKNECPXCLUHT-UHFFFAOYSA-N 0.000 description 1
- KQDJTBPASNJQFQ-UHFFFAOYSA-N 2-iodophenol Chemical compound OC1=CC=CC=C1I KQDJTBPASNJQFQ-UHFFFAOYSA-N 0.000 description 1
- ZTICFRJZFYNHAN-UHFFFAOYSA-N 3-(1-hydroxycyclohexa-2,4-dien-1-yl)prop-2-enoic acid Chemical compound OC(=O)C=CC1(O)CC=CC=C1 ZTICFRJZFYNHAN-UHFFFAOYSA-N 0.000 description 1
- MGGVALXERJRIRO-UHFFFAOYSA-N 4-[2-(2,3-dihydro-1H-inden-2-ylamino)pyrimidin-5-yl]-2-[2-oxo-2-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)ethyl]-1H-pyrazol-5-one Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)C=1C(=NN(C=1)CC(=O)N1CC2=C(CC1)NN=N2)O MGGVALXERJRIRO-UHFFFAOYSA-N 0.000 description 1
- 229920000742 Cotton Polymers 0.000 description 1
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- PEEHTFAAVSWFBL-UHFFFAOYSA-N Maleimide Chemical compound O=C1NC(=O)C=C1 PEEHTFAAVSWFBL-UHFFFAOYSA-N 0.000 description 1
- 239000004677 Nylon Substances 0.000 description 1
- 239000004952 Polyamide Substances 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- 239000004411 aluminium Substances 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 235000010290 biphenyl Nutrition 0.000 description 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 1
- 229910052794 bromium Inorganic materials 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000003618 dip coating Methods 0.000 description 1
- 230000008034 disappearance Effects 0.000 description 1
- WGXGKXTZIQFQFO-CMDGGOBGSA-N ethenyl (e)-3-phenylprop-2-enoate Chemical compound C=COC(=O)\C=C\C1=CC=CC=C1 WGXGKXTZIQFQFO-CMDGGOBGSA-N 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- AMGQUBHHOARCQH-UHFFFAOYSA-N indium;oxotin Chemical compound [In].[Sn]=O AMGQUBHHOARCQH-UHFFFAOYSA-N 0.000 description 1
- MRNHPUHPBOKKQT-UHFFFAOYSA-N indium;tin;hydrate Chemical compound O.[In].[Sn] MRNHPUHPBOKKQT-UHFFFAOYSA-N 0.000 description 1
- 230000001788 irregular Effects 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- RLQOUIUVEQXDPW-UHFFFAOYSA-M lithium;2-methylprop-2-enoate Chemical compound [Li+].CC(=C)C([O-])=O RLQOUIUVEQXDPW-UHFFFAOYSA-M 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 229920001778 nylon Polymers 0.000 description 1
- 239000011368 organic material Substances 0.000 description 1
- NWVVVBRKAWDGAB-UHFFFAOYSA-N p-methoxyphenol Chemical compound COC1=CC=C(O)C=C1 NWVVVBRKAWDGAB-UHFFFAOYSA-N 0.000 description 1
- 238000006303 photolysis reaction Methods 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
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- 229920000515 polycarbonate Polymers 0.000 description 1
- 239000004417 polycarbonate Substances 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 238000005096 rolling process Methods 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000000935 solvent evaporation Methods 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
- C08J7/12—Chemical modification
- C08J7/123—Treatment by wave energy or particle radiation
-
- G—PHYSICS
- G02—OPTICS
- G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
- G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
- G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour
- G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour based on liquid crystals, e.g. single liquid crystal display cells
- G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
- G02F1/1333—Constructional arrangements; Manufacturing methods
- G02F1/1337—Surface-induced orientation of the liquid crystal molecules, e.g. by alignment layers
- G02F1/133711—Surface-induced orientation of the liquid crystal molecules, e.g. by alignment layers by organic films, e.g. polymeric films
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D3/00—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials
- B05D3/02—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials by baking
- B05D3/0254—After-treatment
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D3/00—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials
- B05D3/06—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials by exposure to radiation
- B05D3/061—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials by exposure to radiation using U.V.
- B05D3/065—After-treatment
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
- C08F220/12—Esters of monohydric alcohols or phenols
- C08F220/16—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
- C08F220/18—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms with acrylic or methacrylic acids
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
- C08F220/26—Esters containing oxygen in addition to the carboxy oxygen
- C08F220/30—Esters containing oxygen in addition to the carboxy oxygen containing aromatic rings in the alcohol moiety
- C08F220/303—Esters containing oxygen in addition to the carboxy oxygen containing aromatic rings in the alcohol moiety and one or more carboxylic moieties in the chain
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/18—Manufacture of films or sheets
-
- G—PHYSICS
- G02—OPTICS
- G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
- G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
- G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour
- G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour based on liquid crystals, e.g. single liquid crystal display cells
- G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
- G02F1/1333—Constructional arrangements; Manufacturing methods
- G02F1/1337—Surface-induced orientation of the liquid crystal molecules, e.g. by alignment layers
- G02F1/133711—Surface-induced orientation of the liquid crystal molecules, e.g. by alignment layers by organic films, e.g. polymeric films
- G02F1/133715—Surface-induced orientation of the liquid crystal molecules, e.g. by alignment layers by organic films, e.g. polymeric films by first depositing a monomer
-
- G—PHYSICS
- G02—OPTICS
- G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
- G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
- G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour
- G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour based on liquid crystals, e.g. single liquid crystal display cells
- G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
- G02F1/1333—Constructional arrangements; Manufacturing methods
- G02F1/1337—Surface-induced orientation of the liquid crystal molecules, e.g. by alignment layers
- G02F1/13378—Surface-induced orientation of the liquid crystal molecules, e.g. by alignment layers by treatment of the surface, e.g. embossing, rubbing or light irradiation
- G02F1/133788—Surface-induced orientation of the liquid crystal molecules, e.g. by alignment layers by treatment of the surface, e.g. embossing, rubbing or light irradiation by light irradiation, e.g. linearly polarised light photo-polymerisation
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Abstract
Provided are a method for manufacturing a liquid crystal alignment film for enabling highly efficient anisotropy to be introduced into a film without rubbing, as well as a liquid crystal alignment film and a liquid crystal display element. A method for manufacturing a liquid crystal alignment film having [I] a step for forming, on a substrate, a photosensitive side-chain polymer film exhibiting liquid crystal properties in a predetermined temperature range, [II] a step for irradiating polarized ultraviolet rays to the side-chain polymer film, and [III] a step for heating the side-chain polymer film irradiated with the ultraviolet rays, the method being characterized in that the amount of irradiated ultraviolet rays in step [II] is within 1%-70% of the amount of irradiated ultraviolet rays that maximizes the difference [increment]A between the ultraviolet absorbance in the direction parallel to the polarization direction of the polarized ultraviolet rays and the ultraviolet absorbance in the direction perpendicular thereto in the side-chain polymer film.
Description
Technical field
The present invention relates to manufacture method, liquid crystal orientation film and the liquid crystal display cells of liquid crystal orientation film, the liquid crystal orientation film that particularly relate to the manufacture method of the liquid crystal orientation film using in liquid crystal display cells, obtains by this manufacture method and the liquid crystal display cells that uses this liquid crystal orientation film.
Background technology
Liquid crystal display cells is well-known as light weight, display device slim and low power consumption, is applied in recent years large-scale televisor purposes etc., has obtained alarming development.Liquid crystal display cells is for example clamped liquid crystal layer and forms with the transparent a pair of substrate with electrode.So, in liquid crystal display cells, for making liquid crystal be required state of orientation between substrate, use the organic film being formed by organic material as liquid crystal orientation film.
That is, liquid crystal orientation film is the member of formation of liquid crystal display cells, is formed on the face contacting with liquid crystal of the substrate that liquid crystal is clamped, and plays the effect towards certain orientation orientation at this substrate chien shih liquid crystal.So, for liquid crystal orientation film, except making liquid crystal towards the effect of the certain orientation orientations such as for example parallel with substrate direction, sometimes also require the effect of the tilt angle of controlling liquid crystal.The ability (calling orientation control ability in the following text) of the control liquid crystal aligning of such liquid crystal orientation film is to give by the organic film that forms liquid crystal orientation film is carried out to orientation process.
As the method for orientation treatment of the liquid crystal orientation film for giving orientation control ability, known rubbing manipulation all the time.Rubbing manipulation refers to following method: for organic films such as the polyvinyl alcohol (PVA) on substrate, polyamide, polyimide, use the cloth of cotton, nylon, polyester etc. towards certain orientation wiping (friction) on its surface, make direction (frictional direction) orientation of liquid crystal towards wiping.This rubbing manipulation can realize the state of orientation of comparatively stable liquid crystal easily, therefore in the manufacturing process of existing liquid crystal display cells, has use always.So, as the organic film using in liquid crystal orientation film, mainly select the organic film of the polyimide of the reliabilities such as thermotolerance and electrical characteristics excellence in the past.
But in the rubbing manipulation that the liquid crystal orientation film surface being made up of polyimide etc. is rubbed, the generation of airborne dust and static becomes problem sometimes.In addition, it is concavo-convex that the switch active element of using due to the high-precision refinement of liquid crystal display cells in recent years, by the electrode on corresponding substrate or liquid crystal drive causes, sometimes cannot rub equably to liquid crystal orientation film surface with cloth, cannot realize uniform liquid crystal aligning.
So, as other method for orientation treatment of the liquid crystal orientation film not rubbing, optical alignment method has been carried out to large quantity research.
Optical alignment method has various methods, but is all to utilize the light of rectilinearly polarized light or collimation to form anisotropy in the organic film that forms liquid crystal orientation film, makes liquid crystal aligning along this anisotropy.
As main optical alignment method, the optical alignment method of known breakdown type.For example polyimide film is irradiated to polarized UV rays, utilize the polarization direction dependence of the UVA of molecular structure to make it that anisotropic decomposition occur.Then, utilize undecomposed and residual polyimide to make liquid crystal aligning (with reference to patent documentation 1).
In addition the also optical alignment method of known photo-crosslinking type or photoisomerization type.For example use poly-vinyl cinnamate, irradiate polarized UV rays, at two key part generation dimerizations (cross-linking reaction) of 2 side chains parallel with polarized light.Then, make liquid crystal towards the direction orientation (with reference to non-patent literature 1) orthogonal with polarization direction.In addition, use side chain to have in the high molecular situation of side chain type of azobenzene, irradiate polarized UV rays, in the azobenzene part generation isomerization reaction of the side chain parallel with polarized light, make liquid crystal towards the direction orientation (with reference to non-patent literature 2) orthogonal with polarization direction.
As described in the above example, adopt in the method for orientation treatment of liquid crystal orientation film of optical alignment method, do not need friction, do not worry the generation of airborne dust and static.So, even also can implementation orientation processing for the substrate of the irregular liquid crystal display cells in surface, be the method for orientation treatment that is suitable for the liquid crystal orientation film of the production technology of industrial circle.
Prior art document
Patent documentation
Patent documentation 1: No. 3893659 communique of Jap.P.
Non-patent literature
Non-patent literature 1:M.Shadt etc., Jpn.J.Appl.Phys.31,2155 (1992)
Non-patent literature 2:K.Ichimura etc., Chem.Rev.100,1847 (2000)
Summary of the invention
Invent technical matters to be solved
As mentioned above, optical alignment method with all the time as the method for orientation treatment of liquid crystal display cells compared with the rubbing manipulation of industrial circle application, do not need friction process itself, therefore there is very large advantage.And compared with the rubbing manipulation of orientation control ability constant by friction, optical alignment method can change the exposure of polarized light and control orientation control ability.But, in optical alignment method, when wish realizes with employing rubbing manipulation, in the situation of the orientation control ability of same degree, sometimes need the exposure of a large amount of polarized lights, or cannot realize stable liquid crystal aligning.
For example, in the optical alignment method of breakdown type of recording in above-mentioned patent documentation 1, need to irradiate to polyimide film the ultraviolet light 60 minutes etc. of the high-pressure sodium lamp that derives from output power 500W, need long-time and a large amount of ultraviolet rays to irradiate.In addition,, in the situation of the optical alignment method of dimerization type or photoisomerization type, sometimes also need a large amount of ultraviolet ray of several J (joule)～tens of J left and right to irradiate.Further, in the situation of the optical alignment method of photo-crosslinking type or photoisomerization type, thermal stability and the light stability of the orientation of liquid crystal are poor, have the problem that orientation is bad or screen is burnt in demonstration that occurs while therefore making liquid crystal display cells.
Therefore, in optical alignment method, require to realize the high efficiency of orientation process and stable liquid crystal aligning, require to develop and can give efficiently the manufacture method of liquid crystal orientation film with the liquid crystal orientation film of high orientation control ability.
So, the object of this invention is to provide a kind of manufacture method that can use up the liquid crystal orientation film that carries out efficiently good liquid crystal aligning control.
In addition, the object of this invention is to provide a kind of manufacture method that adopts this liquid crystal orientation film realizes and makes the high efficiency orientation process of using up and the liquid crystal orientation film of making.
Object of the present invention also provide a kind of have realize make the high efficiency orientation process of using up and the liquid crystal display cells of the liquid crystal orientation film of making.
The technical scheme that technical solution problem adopts
The inventor has carried out conscientiously research, and result obtains following discovery, thereby has completed the present invention.
What the manufacture method of liquid crystal orientation film of the present invention adopted is use can embody liquid crystal liquid crystal property photosensitive side chain type polymeric membrane, do not carry out friction treatment but carry out the method for orientation process by polarizing light irradiation.Then, after polarizing light irradiation, the operation to this side chain type polymeric membrane heating is set, manufactures liquid crystal orientation film.Now, by the heating-up temperature in the heating process after exposure and the polarizing light irradiation of optimization polarized light, can realize high efficiency orientation process by liquid crystal orientation film, can give good orientation control ability with high-level efficiency.
The present invention has following technology contents.
(1) manufacture method for liquid crystal orientation film, it comprises:
[I] is formed on the operation that embodies the photosensitive side chain type polymeric membrane of liquid crystal liquid crystal property in the temperature range of regulation on substrate;
[II] irradiates the operation of polarized UV rays to described side chain type polymeric membrane; And
[III] operation to the side chain type polymeric membrane heating of irradiating through described ultraviolet ray;
It is characterized in that, the ultraviolet irradiation amount of [II] operation is in Δ A reaches 1%～70% scope of maximum ultraviolet irradiation amount, and Δ A is the poor of the ultraviolet absorbance of described side chain type polymeric membrane, the direction parallel with the polarization direction of described polarized UV rays and the ultraviolet absorbance of the direction vertical with the polarization direction of described polarized UV rays.
(2) manufacture method of above-mentioned (1) described liquid crystal orientation film, wherein, the ultraviolet irradiation amount of [II] operation is in described Δ A reaches 1%～50% scope of maximum ultraviolet irradiation amount.
(3) manufacture method of the liquid crystal orientation film described in above-mentioned (1) or (2), wherein, the heating-up temperature of [III] operation is to embody the temperature of 10 DEG C of the lower limits for height of the temperature range of liquid crystal liquid crystal property～than the temperature in the scope of the temperature of low 10 DEG C of the upper limit of this temperature range than described side chain type polymeric membrane.
(4) manufacture method of the liquid crystal orientation film described in any one in above-mentioned (1)～(3), wherein, described in, embodying contained photonasty group in the photosensitive side chain type macromolecule of liquid crystal liquid crystal property is azobenzene, Stilbene, cinnamic acid, cinnamate, chalcone, cumarin, tolane, phenol benzoate or derivatives thereof.
(5) manufacture method for liquid crystal orientation film, it comprises:
[I] is formed on the operation that embodies the side chain type polymeric membrane of the photocrosslinking reaction of liquid crystal liquid crystal property in the temperature range of regulation on substrate;
[II] irradiates the operation of polarized UV rays to described photocrosslinking reaction side chain type polymeric membrane; And
[III] operation to the side chain type polymeric membrane heating of irradiating through described ultraviolet ray;
[IV] was to irradiating described ultraviolet ray, then irradiating unpolarized ultraviolet operation through the side chain type polymeric membrane of heating;
It is characterized in that, the ultraviolet irradiation amount of [II] operation is in Δ A reaches 1%～70% scope of maximum ultraviolet irradiation amount, and Δ A is the poor of the ultraviolet absorbance of described side chain type polymeric membrane, the direction parallel with the polarization direction of described polarized UV rays and the ultraviolet absorbance of the direction vertical with the polarization direction of described polarized UV rays.
(6) manufacture method of above-mentioned (5) described liquid crystal orientation film, wherein, the ultraviolet irradiation amount of [II] operation is in described Δ A reaches 1%～50% scope of maximum ultraviolet irradiation amount.
(7) manufacture method of the liquid crystal orientation film described in above-mentioned (5) or (6), wherein, the heating-up temperature of [III] operation is to embody the temperature of 10 DEG C of the lower limits for height of the temperature range of liquid crystal liquid crystal property～than the temperature in the scope of the temperature of low 10 DEG C of the upper limit of this temperature range than described side chain type polymeric membrane.
(8) manufacture method of the liquid crystal orientation film described in any one in above-mentioned (5)～(7), wherein, ultraviolet ray by [IV] operation is irradiated, and 20 % by mole of the photocrosslinking reaction group that described side chain type polymeric membrane has react above.
(9) manufacture method of the liquid crystal orientation film described in any one in above-mentioned (5)～(8), wherein, described in, embodying contained photonasty group in the side chain type macromolecule of photocrosslinking reaction of liquid crystal liquid crystal property is cinnamic acid, cinnamate, chalcone, cumarin, tolane or derivatives thereof.
(10) manufacture method of the liquid crystal orientation film described in any one in above-mentioned (1)～(9), wherein, described side chain type polymeric membrane is the structure that comprises main chain and side chain, described main chain is made up of at least one that is selected from hydrocarbon, acrylate and methacrylate, and described side chain represents with at least one in following formula (1)～(7);
[changing 1]
In formula (1), A
1, B
1represent independently respectively singly-bound ,-O-,-CH
2-,-COO-,-OCO-,-CONH-or NH-CO-, Y
1be at least one group that is selected from the cyclic hydrocarbon of phenyl ring, naphthalene nucleus, cyclohexyl biphenyl, furan nucleus, pyrrole ring and carbon number 5～8, on these groups, the hydrogen atom of bonding can be distinguished independently by-NO
2,-CN ,-C=C (CN)
2,-C=CH-CN, halogen group, alkyl or alkoxy replace; X
1represent singly-bound ,-COO-,-OCO-,-N=N-,-C=C-,-C ≡ C-or C
6h
4-, l1 (also claims l
1) representing 1～12 integer, m1 represents 1～3 integer, n1 represents 1～12 integer; In formula (2), A
2, B
2, D
1represent independently respectively singly-bound ,-O-,-CH
2-,-COO-,-OCO-,-CONH-or NH-CO-, Y
2be at least one group that is selected from the cyclic hydrocarbon of phenyl ring, naphthalene nucleus, cyclohexyl biphenyl, furan nucleus, pyrrole ring and carbon number 5～8, on these groups, the hydrogen atom of bonding can be distinguished independently by-NO
2,-CN ,-C=C (CN)
2,-C=CH-CN, halogen group, alkyl or alkoxy replace; X
2represent singly-bound ,-COO-,-OCO-,-N=N-,-C=C-,-C ≡ C-or C
6h
4-, R
1represent the alkyl of hydrogen atom or carbon number 1～6; L2 (also claims l
2) representing 1～12 integer, m2 represents 1～3 integer, n2 represents 1～12 integer; In formula (3), A
3represent singly-bound ,-O-,-CH
2-,-COO-,-OCO-,-CONH-or NH-CO-, X
3represent singly-bound ,-COO-,-OCO-,-N=N-,-C=C-,-C ≡ C-or C
6h
4-, R
2represent the alkyl of hydrogen atom or carbon number 1～6; L3 (also claims l
3) representing 1～12 integer, m3 represents 1～3 integer; In formula (4), l4 (also claims l
4) represent 1～12 integer; In formula (5), A
4represent singly-bound ,-O-,-CH
2-,-COO-,-OCO-,-CONH-or NH-CO-, X
4expression-COO-, Y
3be at least one group that is selected from phenyl ring, naphthalene nucleus and cyclohexyl biphenyl, on these groups, the hydrogen atom of bonding can be distinguished independently by-NO
2,-CN ,-C=C (CN)
2,-C=CH-CN, halogen group, alkyl or alkoxy replace; L5 (also claims l
5) representing 1～12 integer, m4 represents 1～3 integer; In formula (6), A
5represent singly-bound ,-O-,-CH
2-,-COO-,-OCO-,-CONH-or NH-CO-, R
3represent to be selected from hydrogen atom ,-NO
2,-CN ,-C=C (CN)
2at least one group of the alkyl of ,-C=CH-CN, halogen group, carbon number 1～6 and the alkoxy of carbon number 1～6; L6 (also claims l
6) represent 1～12 integer; On phenyl ring in formula (6), the hydrogen atom of bonding can be distinguished independently by-NO
2,-CN ,-C=C (CN)
2,-C=CH-CN, halogen group, alkyl or alkoxy replace; In formula (7), A
6represent singly-bound ,-O-,-CH
2-,-COO-,-OCO-,-CONH-or NH-CO-, B
3represent singly-bound ,-COO-,-OCO-,-N=N-,-C=C-,-C ≡ C-or C
6h
4-; W
1be at least one group that is selected from the cyclic hydrocarbon of phenyl ring, naphthalene nucleus, cyclohexyl biphenyl, furan nucleus, pyrrole ring and carbon number 5～8, on these groups, the hydrogen atom of bonding can be distinguished independently by-NO
2,-CN ,-C=C (CN)
2,-C=CH-CN, halogen group, alkyl or alkoxy replace; L7 represents 1～12 integer, and m5, m6 represent respectively 1～3 integer.
(11) liquid crystal orientation film, its manufacture method by the liquid crystal orientation film described in any one in above-mentioned (1)～(10) is made.
(12) liquid crystal display cells, it has above-mentioned (11) described liquid crystal orientation film.
The effect of invention
By the present invention, can provide a kind of manufacture method of the liquid crystal orientation film that can realize high efficiency orientation process.
In addition, adopt the manufacture method of this liquid crystal orientation film, a kind of liquid crystal orientation film that can realize high efficiency orientation process can be provided.Adopt this liquid crystal orientation film, a kind of liquid crystal display cells with the liquid crystal orientation film of realizing high efficiency orientation process and make also can be provided.
Brief description of the drawings
Fig. 1 be pattern the figure of the example that describes of anisotropic introducing processing in the manufacture method of liquid crystal orientation film to the first form of the present invention.(a) be pattern represent the figure of the state of the side chain type polymeric membrane before polarizing light irradiation, situation that the anisotropy particularly introduced is little, the i.e. mode chart of the ultraviolet irradiation amount of [II] operation in the manufacture method of the liquid crystal orientation film that comprises above-mentioned [I]～[IV] operation of the present invention situation in Δ A reaches 1%～15% scope of maximum ultraviolet irradiation amount.(b) be pattern represent the figure of the state of the side chain type polymeric membrane after polarizing light irradiation, (c) be pattern represent the figure of state of the side chain type polymeric membrane after heating, figure (d) be pattern represent after heating the figure through the state of unpolarized light-struck side chain type polymeric membrane.To above-mentioned the first form as described later.
Fig. 2 be pattern the figure of the example that describes of anisotropic introducing processing in the manufacture method of liquid crystal orientation film to the first form of the present invention, situation that the anisotropy particularly introduced is large, the i.e. mode chart of the ultraviolet irradiation amount of [II] operation in the manufacture method of the liquid crystal orientation film that comprises above-mentioned [I]～[IV] operation of the present invention situation in Δ A reaches 15%～70% scope of maximum ultraviolet irradiation amount.(a) be pattern represent the figure of the state of the side chain type polymeric membrane before polarizing light irradiation, (b) be pattern represent the figure of the state of the side chain type polymeric membrane after polarizing light irradiation, (c) be pattern represent the figure of state of the side chain type polymeric membrane after heating, figure (d) be pattern represent after heating the figure through the state of unpolarized light-struck side chain type polymeric membrane.
Fig. 3 be pattern the figure, particularly side chain type macromolecule of the example that describes of anisotropic introducing processing in the manufacture method of liquid crystal orientation film to the second form of the present invention be the situation of the structure that represents of above formula (6), in the manufacture method that comprises above-mentioned [I]～[III] operation of the present invention, when the side chain type polymeric membrane of the structure that represents of use formula (6), the mode chart of the ultraviolet irradiation amount of [II] operation situation in Δ A reaches 1%～70% scope of maximum ultraviolet irradiation amount.(a) be pattern represent the figure of the state of the side chain type polymeric membrane before polarizing light irradiation, (b) be pattern represent the figure of the state of the side chain type polymeric membrane after polarizing light irradiation, be (c) pattern represent the figure of the state of the side chain type polymeric membrane after heating.To above-mentioned the second form as described later.
Fig. 4 be pattern the figure, particularly side chain type macromolecule of the example that describes of anisotropic introducing processing in the manufacture method of liquid crystal orientation film to the second form of the present invention be the situation of the structure that represents of above formula (7), in the manufacture method that comprises above-mentioned [I]～[III] operation of the present invention, when the side chain type macromolecule of the structure that represents of use formula (7), the mode chart of the ultraviolet irradiation amount of [II] operation situation in Δ A reaches 1%～70% scope of maximum ultraviolet irradiation amount.(a) be pattern represent the figure of the state of the side chain type polymeric membrane before polarizing light irradiation, (b) be pattern represent the figure of the state of the side chain type polymeric membrane after polarizing light irradiation, be (c) pattern represent the figure of the state of the side chain type polymeric membrane after heating.
Embodiment
The photosensitive side chain type polymeric membrane using in the manufacture method of liquid crystal orientation film of the present invention, can embody liquid crystal liquid crystal property is the photosensitive side chain type polymeric membrane that embodies liquid crystal liquid crystal property in the temperature range of regulation.And the side chain of bonding has photonasty on main chain, can sense light and cross-linking reaction, isomerization reaction or light fries' rearrangement occur.On main chain, the photosensitive group that has of bonding is not particularly limited, and preferably senses light and the structure of cross-linking reaction or light fries' rearrangement occurs.Now, even if be exposed to the external pressures such as heat, also can keep steadily in the long term realized orientation control ability.Meet this characteristic and be just not particularly limited as long as can embody the structure of the photosensitive side chain type polymeric membrane of liquid crystal liquid crystal property, in preferential side chain structure, there is the primitive composition (Japanese: メ ソ ゲ Application composition) of rigidity.
Now, when this side chain type macromolecule is made to liquid crystal orientation film, can obtain stable liquid crystal aligning.This high molecular structure example be as can be comprise main chain and have the primitive compositions such as xenyl, terphenyl base, benzyl ring hexyl, phenylamino benzoic acid ester group, azobenzene with side chain, this side chain of its bonding and be bonded in leading section, sense light and carry out the structure of the photonasty group of cross-linking reaction or isomerization reaction, or can be comprise main chain and with side chain, this side chain of its bonding be also primitive composition and the structure with the phenylamino benzoic acid ester group that carries out light Fries rearrangement.
As the example more specifically of structure of photosensitive side chain type polymeric membrane that can embody liquid crystal liquid crystal property, preferably include by being selected from least one main chain forming of hydrocarbon, acrylate, methacrylate, maleimide and cyclohexane and the structure by the side chain of at least one formation in following formula (1)～(7).
[changing 2]
(the A in formula (1)
1, B
1, X
1, Y
1, l1, m1, n1 be as above definition, the A in formula (2)
2, B
2, D
1, X
2, Y
2, R
1, l2, m2, n2 be as above definition, the A in formula (3)
3, X
3, R
2, l3, m3 as above definition, the l4 in formula (4) as above definition, the A in formula (5)
4, X
4, Y
3, l5, m4 as above definition, the A in formula (6)
5, R
3, l6 as above definition.A in formula (7)
6, B
3, W
1, l7, m5, m6 be as above definition.)
The side chain that above formula (1)～(7) represent comprise there is biphenyl, the group such as terphenyl, benzyl ring hexyl, phenol benzoate, azobenzene is as the structure of primitive composition.And, its leading section have in following structure at least any one,, have and sense light and dimerization occurs, carry out the photonasty group of cross-linking reaction, or comprise main chain and be also primitive composition and there is the phenylamino benzoic acid ester group that carries out light Fries rearrangement with side chain, this side chain of its bonding.
In the present invention, side chain type polymeric membrane can be not losing in liquid crystal liquid crystal property and photoreactive scope and not having photoreactive side-chain structure and use.If for example, can exemplify the structure of following formula (8).
[changing 3]
In above formula (8), E
1represent singly-bound ,-O-,-CH
2-,-COO ,-OCO-,-CONH-,-NH-CO-, Z represents singly-bound ,-COO ,-OCO-,-N=N-,-C=C-,-C ≡ C-or C
6h
4-, k1 represents 1～12 integer, p1, q1 represent respectively 0～3 integer, R independently
4represent hydrogen atom ,-NO
2,-CN ,-C=C (CN)
2alkoxy, the carboxyl of ,-C=CH-CN, halogen group, carbon number 1～6 or the group being combined by it.
Below, the photosensitive side chain type polymeric membrane using in the manufacture method for liquid crystal orientation film of the present invention, can embody liquid crystal liquid crystal property, by it referred to as side chain type polymeric membrane of the present invention.
In the manufacture method of liquid crystal orientation film of the present invention, on substrate, form after film with side chain type macromolecule of the present invention, irradiate polarized UV rays.Then, in side chain type polymeric membrane, introduce anisotropy efficiently by heating, make the liquid crystal orientation film of the orientation control ability with liquid crystal.In the manufacture method of liquid crystal orientation film of the present invention, utilize the light reaction of side chain type polymeric membrane of the present invention and the principle of the molecular reorientation of bringing out by the self assembly based on liquid crystal liquid crystal property, in side chain type polymeric membrane, introduce anisotropy efficiently.Also have, in the manufacture method of liquid crystal orientation film of the present invention, to have in the situation of photocrosslinking reaction group as the structure of photoreactive group, on substrate, form after film with side chain type macromolecule of the present invention, irradiate polarized UV rays, then, after heating, irradiate unpolarized ultraviolet ray, by this can be by the anisotropy immobilization of introducing in polymeric membrane.
Fig. 1 be pattern in the manufacture method of liquid crystal orientation film of the present invention, use the figure with the example that photocrosslinking reaction group describes as the anisotropic introducing processing in the manufacture method of the high molecular liquid crystal orientation film of side chain type of the structure of photoreactive group.Fig. 1 (a) be pattern represent the figure of the state of the side chain type polymeric membrane before polarizing light irradiation, Fig. 1 (b) be pattern represent the figure of the state of the side chain type polymeric membrane after polarizing light irradiation, Fig. 1 (c) be pattern represent the figure of state of the side chain type polymeric membrane after heating, Fig. 1 (d) be pattern represent the figure of the state of the postradiation side chain type polymeric membrane of nonpolarized light, the little situation of anisotropy of particularly introducing, it is the mode chart of the ultraviolet irradiation amount of [II] operation in the manufacture method of the liquid crystal orientation film that comprises above-mentioned [I]～[IV] operation of the present invention situation in Δ A reaches 1%～15% scope of maximum ultraviolet irradiation amount.
Fig. 2 be pattern in the manufacture method of liquid crystal orientation film of the present invention, use the figure with the example that photocrosslinking reaction group describes as the anisotropic introducing processing in the manufacture method of the high molecular liquid crystal orientation film of side chain type of the structure of photoreactive group.Fig. 2 (a) be pattern represent the figure of the state of the side chain type polymeric membrane before polarizing light irradiation, Fig. 2 (b) be pattern represent the figure of the state of the side chain type polymeric membrane after polarizing light irradiation, Fig. 2 (c) be pattern represent the figure of state of the side chain type polymeric membrane after heating, Fig. 2 (d) be pattern represent the figure of the state of the postradiation side chain type polymeric membrane of nonpolarized light, the large situation of anisotropy of particularly introducing, it is the mode chart of the ultraviolet irradiation amount of [II] operation in the manufacture method of the liquid crystal orientation film that comprises above-mentioned [I]～[IV] operation of the present invention situation in Δ A reaches 15%～70% scope of maximum ultraviolet irradiation amount.
Fig. 3 be pattern in the manufacture method of liquid crystal orientation film of the present invention, use the figure with the example that describes as the anisotropic introducing processing in the manufacture method of the high molecular liquid crystal orientation film of side chain type of the structure of photoreactive group of light fries' rearrangement group that above formula (6) represents.Fig. 3 (a) be pattern represent the figure of the state of the side chain type polymeric membrane before polarizing light irradiation, Fig. 3 (b) be pattern represent the figure of the state of the side chain type polymeric membrane after polarizing light irradiation, Fig. 3 (c) be pattern represent the figure of state of the side chain type polymeric membrane after heating, situation that the anisotropy particularly introduced is little, the i.e. mode chart of the ultraviolet irradiation amount of [II] operation in the manufacture method that comprises above-mentioned [I]～[III] operation of the present invention situation in Δ A reaches 1%～70% scope of maximum ultraviolet irradiation amount.
Fig. 4 be pattern in the manufacture method of liquid crystal orientation film of the present invention, use the figure with the example that describes as the anisotropic introducing processing in the manufacture method of the high molecular liquid crystal orientation film of side chain type of the structure of photoreactive group of light fries' rearrangement group that above formula (7) represents.Fig. 4 (a) be pattern represent the figure of the state of the side chain type polymeric membrane before polarizing light irradiation, Fig. 4 (b) be pattern represent the figure of the state of the side chain type polymeric membrane after polarizing light irradiation, Fig. 4 (c) be pattern represent the figure of state of the side chain type polymeric membrane after heating, situation that the anisotropy particularly introduced is large, the i.e. mode chart of the ultraviolet irradiation amount of [II] operation in the manufacture method that comprises above-mentioned [I]～[III] operation of the present invention situation in Δ A reaches 1%～70% scope of maximum ultraviolet irradiation amount.
Below, use is had to photocrosslinking reaction group and be called the first form as the high molecular embodiment of side chain type of the structure of photoreactive group, use is had to light fries' rearrangement group and be called the second form as the high molecular embodiment of side chain type of the structure of photoreactive group, describe.
Anisotropic introducing processing in side chain type polymeric membrane in the manufacture method of the liquid crystal orientation film by the first form of the present invention, the ultraviolet irradiation amount of [II] operation, in the case of in Δ A reaches 1%～15% scope of maximum ultraviolet irradiation amount, first forms side chain type polymeric membrane 1 of the present invention on substrate.As shown in Fig. 1 (a), be formed on side chain type polymeric membrane 1 of the present invention on substrate and have the structure of side chain 2 random alignment.Along the random alignment of the side chain 2 of side chain type polymeric membrane 1, the primitive composition of side chain 2 and also random orientation of photonasty group, this side chain type polymeric membrane 1 is isotropy.
Anisotropic introducing processing in side chain type polymeric membrane in the manufacture method of the liquid crystal orientation film by the first form of the present invention, the ultraviolet irradiation amount of [II] operation, in the case of in Δ A reaches 15%～70% scope of maximum ultraviolet irradiation amount, first forms the side chain type polymeric membrane 3 of present embodiment on substrate.As shown in Fig. 2 (a), be formed on side chain type polymeric membrane 3 of the present invention on substrate and have the structure of side chain 4 random alignment.Along the random alignment of the side chain 4 of side chain type polymeric membrane 3, the primitive composition of side chain 4 and also random orientation of photonasty group, this side chain type polymeric membrane 2 is isotropy.
Anisotropic introducing processing in side chain type polymeric membrane in the manufacture method of the liquid crystal orientation film by the second form of the present invention, adopt in the situation of the high molecular liquid crystal orientation film of side chain type of the structure that uses the light fries' rearrangement group with above formula (6) expression, the ultraviolet irradiation amount of [II] operation, in the case of in Δ A reaches 1%～70% scope of maximum ultraviolet irradiation amount, first forms side chain type polymeric membrane 5 of the present invention on substrate.As shown in Fig. 3 (a), be formed on side chain type polymeric membrane 5 of the present invention on substrate and have the structure of side chain 6 random alignment.Along the random alignment of the side chain 6 of side chain type polymeric membrane 5, the primitive composition of side chain 6 and also random orientation of photonasty group, this side chain type polymeric membrane 5 is isotropy.
Anisotropic introducing processing in side chain type polymeric membrane in the manufacture method of the liquid crystal orientation film by the second form of the present invention, adopt use have light fries' rearrangement group that above formula (7) represents as the situation of the high molecular liquid crystal orientation film of side chain type of structure under, the ultraviolet irradiation amount of [II] operation, in the case of in Δ A reaches 1%～70% scope of maximum ultraviolet irradiation amount, first forms side chain type polymeric membrane 7 of the present invention on substrate.As shown in Fig. 4 (a), be formed on side chain type polymeric membrane 7 of the present invention on substrate and have the structure of side chain 8 random alignment.Along the random alignment of the side chain 8 of side chain type polymeric membrane 7, the primitive composition of side chain 8 and also random orientation of photonasty group, this side chain type polymeric membrane 7 is isotropy.
In the first form of the present invention, the ultraviolet irradiation amount of [II] operation, in the case of in Δ A reaches 1%～15% scope of maximum ultraviolet irradiation amount, irradiates polarized UV rays to this isotropic side chain type polymeric membrane 1 of the present invention.So as shown in Fig. 1 (b), preferentially there is the light reactions such as dimerization in the photonasty group of the side chain 2a with photonasty group in the side chain 2 of arranging in the direction parallel with ultraviolet polarization direction.Consequently, the density of the side chain 2a after light reaction slightly raises on the polarization direction of irradiation ultraviolet radiation, and result is given side chain type polymeric membrane 1 of the present invention with very little anisotropy.
In the first form of the present invention, the ultraviolet irradiation amount of [II] operation, in the case of in Δ A reaches 15%～70% scope of maximum ultraviolet irradiation amount, irradiates polarized UV rays to this isotropic side chain type polymeric membrane 3 of the present invention.So as shown in Fig. 2 (b), preferentially there is the light reactions such as dimerization in the photonasty group of the side chain 4a with photonasty group in the side chain 4 of arranging in the direction parallel with ultraviolet polarization direction.Consequently, the density of the side chain 4a after light reaction raises on the polarization direction of irradiation ultraviolet radiation, and result is given side chain type polymeric membrane 3 of the present invention with less anisotropy.
In the second form of the present invention, adopt in the situation of the high molecular liquid crystal orientation film of side chain type of the structure that uses the light fries' rearrangement group with above formula (6) expression, the ultraviolet irradiation amount of [II] operation, in the case of in Δ A reaches 1%～70% scope of maximum ultraviolet irradiation amount, irradiates polarized UV rays to this isotropic side chain type polymeric membrane 5 of the present invention.So as shown in Fig. 3 (b), preferentially there is the light reactions such as light fries' rearrangement in the photonasty group of the side chain 6a with photonasty group in the side chain 6 of arranging in the direction parallel with ultraviolet polarization direction.Consequently, the density of the side chain 6a after light reaction slightly raises on the polarization direction of irradiation ultraviolet radiation, and result is given side chain type polymeric membrane 5 of the present invention with very little anisotropy.
In the second form of the present invention, adopt in the situation of the high molecular liquid crystal orientation film of side chain type of the structure that uses the light fries' rearrangement group with above formula (7) expression, the ultraviolet irradiation amount of [II] operation, in the case of in Δ A reaches 1%～70% scope of maximum ultraviolet irradiation amount, irradiates polarized UV rays to this isotropic side chain type polymeric membrane 7 of the present invention.So as shown in Fig. 4 (b), preferentially there is the light reactions such as light fries' rearrangement in the photonasty group of the side chain 8a with photonasty group in the side chain 8 of arranging in the direction parallel with ultraviolet polarization direction.Consequently, the density of the side chain 8a after light reaction raises on the polarization direction of irradiation ultraviolet radiation, and result is given side chain type polymeric membrane 7 of the present invention with less anisotropy.
Then, in the first form of the present invention, the ultraviolet irradiation amount of [II] operation, in the case of in Δ A reaches 1%～15% scope of maximum ultraviolet irradiation amount, heats the side chain type polymeric membrane 1 of the present invention after polarizing light irradiation, makes it be mesomorphic state.So as shown in Fig. 1 (c), in side chain type polymeric membrane 1, between the direction parallel with the polarization direction of irradiation ultraviolet radiation and vertical direction, the amount of the cross-linking reaction of generation is different.Now, the amount of the cross-linking reaction occurring in the direction parallel with the polarization direction of irradiation ultraviolet radiation is very little, and therefore the effect of plastifier is played at this cross-linking reaction position.Therefore, the liquid crystal liquid crystal property of the direction vertical with the polarization direction of irradiation ultraviolet radiation is higher than the liquid crystal liquid crystal property of parallel direction, self assembly in the direction parallel with the polarization direction of irradiation ultraviolet radiation, and there is reorientation in the side chain 2 that comprises primitive composition.Consequently, the very little anisotropy of the side chain type polymeric membrane 1 of the present invention being brought out by photo-crosslinking is exaggerated under the effect of heat, thereby gives side chain type polymeric membrane 1 of the present invention with larger anisotropy.
Similarly, in the first form of the present invention, the ultraviolet irradiation amount of [II] operation, in the case of in Δ A reaches 15%～70% scope of maximum ultraviolet irradiation amount, heats the side chain type polymeric membrane 3 of the present invention after polarizing light irradiation, makes it be mesomorphic state.So as shown in Fig. 2 (c), in side chain type polymeric membrane 3, between the direction parallel with the polarization direction of irradiation ultraviolet radiation and vertical direction, the amount of the cross-linking reaction of generation is different.Therefore, self assembly in the direction parallel with the polarization direction of irradiation ultraviolet radiation, there is reorientation in the side chain 4 that comprises primitive composition.Consequently, the less anisotropy of the side chain type polymeric membrane 3 of the present invention being brought out by photo-crosslinking is exaggerated under the effect of heat, thereby gives side chain type polymeric membrane 3 of the present invention with larger anisotropy.
Similarly, in the second form of the present invention, adopt in the situation of the high molecular liquid crystal orientation film of side chain type of the structure that uses the light fries' rearrangement group with above formula (6) expression, the ultraviolet irradiation amount of [II] operation is in the case of in Δ A reaches 1%～70% scope of maximum ultraviolet irradiation amount, side chain type polymeric membrane 5 of the present invention after polarizing light irradiation is heated, make it be mesomorphic state.So as shown in Fig. 3 (c), in side chain type polymeric membrane 5, between the direction parallel with the polarization direction of irradiation ultraviolet radiation and vertical direction, the amount of the light Fries rearrangement of generation is different.Now, the liquid crystal aligning power of the side chain before the liquid crystal aligning force rate of the light fries' rearrangement body generating in the direction vertical with the polarization direction of irradiation ultraviolet radiation is reacted is strong, therefore self assembly in the direction vertical with the polarization direction of irradiation ultraviolet radiation, there is reorientation in the side chain 6 that comprises primitive composition.Consequently, the very little anisotropy of the side chain type polymeric membrane 5 of the present invention being brought out by light Fries rearrangement is exaggerated under the effect of heat, thereby gives side chain type polymeric membrane 5 of the present invention with larger anisotropy.
Similarly, in the second form of the present invention, adopt in the situation of the high molecular liquid crystal orientation film of side chain type of the structure that uses the light fries' rearrangement group with above formula (7) expression, the ultraviolet irradiation amount of [II] operation is in the case of in Δ A reaches 1%～70% scope of maximum ultraviolet irradiation amount, side chain type polymeric membrane 7 of the present invention after polarizing light irradiation is heated, make it be mesomorphic state.So as shown in Fig. 4 (c), in side chain type polymeric membrane 7, between the direction parallel with the polarization direction of irradiation ultraviolet radiation and vertical direction, the amount of the light Fries rearrangement of generation is different.The anchor force of light fries' rearrangement body 8 (a) is than the side chain Final 8 before resetting, if therefore generate certain light fries' rearrangement body more than ormal weight, self assembly in the direction parallel with the polarization direction of irradiation ultraviolet radiation, there is reorientation in the side chain 8 that comprises primitive composition.Consequently, the less anisotropy of the side chain type polymeric membrane 7 of the present invention being brought out by light Fries rearrangement is exaggerated under the effect of heat, thereby gives side chain type polymeric membrane 7 of the present invention with larger anisotropy.
Also have, in the first form of the present invention, as shown in Fig. 1 (d) and Fig. 2 (d), the high molecular photoreactive group of side chain type of the present invention is in the situation of photocrosslinking reaction group, self assembly by primitive as shown in Fig. 1 (c) and Fig. 2 (c) and in side chain polymeric membrane after Induced Anisotropy, carry out nonpolarized light irradiation, by this by the immobilization of anisotropy largely of bringing out.
Therefore,, in the manufacture method of liquid crystal orientation film of the present invention, irradiate by the nonpolarized light carrying out successively after the heat treated in the situation of polarized UV rays irradiation to side chain type polymeric membrane of the present invention and heat treated and the first form of the present invention.Can obtain efficiently and introduce anisotropic liquid crystal orientation film.
And, in the manufacture method of liquid crystal orientation film of the present invention, the heating-up temperature in exposure and the heat treated of the polarized UV rays of optimization to side chain type polymeric membrane of the present invention.By this, can in side chain type polymeric membrane, introduce anisotropy efficiently.
The inventor, after conscientiously studying, has obtained following knowledge., introducing anisotropic optimal polarization ultraviolet irradiation amount and the amount that makes photonasty group in this side chain type polymeric membrane carry out photo-crosslinking, photoisomerization reaction or light Fries rearrangement to side chain type polymeric membrane of the present invention efficiently, to reach the exposure of best polarized UV rays corresponding.The result of side chain type polymeric membrane of the present invention being irradiated to polarized UV rays is, if it is few to carry out the photonasty group of side chain of photo-crosslinking, photoisomerization reaction or light Fries rearrangement, do not reach enough light reaction amounts.Now, also cannot carry out sufficient self assembly even if heat subsequently.
On the other hand, in side chain type polymeric membrane of the present invention, be that, if it is excessive to carry out the photonasty group of side chain of cross-linking reaction, the cross-linking reaction on side chain is excessively carried out to the result of the structured illumination polarized UV rays with photocrosslinking reaction group.Now, the film of gained is rigidity, hinders sometimes the carrying out of the self assembly of implementing by heating subsequently.In addition, in side chain type polymeric membrane of the present invention, result to the structured illumination polarized UV rays with light fries' rearrangement group is, if it is excessive to carry out the photonasty group of side chain of light Fries rearrangement, the liquid crystal liquid crystal property of side chain type polymeric membrane excessively reduces.Now, the liquid crystal liquid crystal property of the film of gained also reduces, and hinders sometimes the carrying out of the self assembly of implementing by heating subsequently.And, to having in the situation of structured illumination polarized UV rays of light fries' rearrangement group, if ultraviolet irradiation amount is too much, side chain type macromolecule generation photodissociation of the present invention, the carrying out of the self assembly that obstruction is implemented by heating subsequently sometimes.
Therefore, in side chain type polymeric membrane of the present invention, by the irradiation of polarized UV rays, the best amount that the photonasty group of side chain carries out the reaction of photo-crosslinking, photoisomerization or light Fries rearrangement is preferably 0.1 % by mole～40 % by mole of photonasty group that this side chain type polymeric membrane has, more preferably 0.1 % by mole～20 % by mole.In the present invention, by making the amount of photonasty group of the side chain that carries out light reaction within the scope of this, the self assembly by heat treated is subsequently carried out efficiently, can in film, form efficiently anisotropy.
In the manufacture method of liquid crystal orientation film of the present invention, the optimization of the exposure by polarized UV rays, optimizes the amount of photo-crosslinking, photoisomerization reaction or the light Fries rearrangement of the photonasty group on the side chain of side chain type polymeric membrane.So, add heat treated subsequently, can in side chain type polymeric membrane, introduce anisotropy efficiently.Now, about the amount of suitable polarized UV rays, the evaluation of uv absorption that can be based on side chain type polymeric membrane of the present invention is carried out.
That is, for side chain type polymeric membrane of the present invention, the UVA of the UVA of measuring respectively postradiation, parallel with the polarization direction of the polarized UV rays direction of polarized UV rays and the direction vertical with the polarization direction of polarized UV rays.Evaluate Δ A according to the measurement result of uv absorption, this Δ A is the poor of the ultraviolet absorbance of this side chain type polymeric membrane, the direction parallel with the polarization direction of polarized UV rays and the ultraviolet absorbance of the direction vertical with the polarization direction of polarized UV rays.Then, obtain the maximal value (Δ Amax) of the Δ A realizing in side chain type polymeric membrane of the present invention and realize the exposure of this peaked polarized UV rays.In the manufacture method of liquid crystal orientation film of the present invention, can determine the preferred polarized UV rays amount of irradiating in the manufacture process of liquid crystal orientation film taking the polarized UV rays exposure that realizes this Δ Amax as benchmark.
In the manufacture method of liquid crystal orientation film of the present invention, the exposure of the polarized UV rays to side chain type polymeric membrane of the present invention is preferably in 1%～70% the scope of amount of polarized UV rays that realizes Δ Amax, more preferably in 1%～50% scope.In side chain type polymeric membrane of the present invention, the exposure that realizes the polarized UV rays in 1%～50% the scope of amount of the polarized UV rays of Δ Amax is equivalent to make 0.1 % by mole～20 % by mole of all photonasty groups that this side chain type polymeric membrane has to carry out the amount of the polarized UV rays of photo-crosslinking.
Then, in the manufacture method of liquid crystal orientation film of the present invention, side chain type polymeric membrane of the present invention is irradiated after polarized UV rays, carry out the heating of this side chain type polymeric membrane.Side chain type polymeric membrane of the present invention is the polymeric membrane that can embody liquid crystal liquid crystal property in the temperature range of regulation.The postradiation heat treated of polarized UV rays can be determined as benchmark taking the temperature of the liquid crystal liquid crystal property that embodies this side chain type polymeric membrane., the postradiation heating-up temperature of polarized UV rays preferably embodies the temperature of 10 DEG C of the lower limits for height of the temperature range (calling liquid crystal temperature range in the following text) of liquid crystal liquid crystal property～than the temperature in the scope of the temperature of low 10 DEG C of the upper limit of this liquid crystal temperature range than side chain type polymeric membrane of the present invention.
Side chain type polymeric membrane of the present invention is heated afterwards in the irradiation of polarized UV rays, becomes mesomorphic state, and self assembly in the direction parallel with polarization direction, reorientation occurs.The less anisotropy of the side chain type polymeric membrane of the present invention consequently, being brought out by photo-crosslinking, photoisomerization reaction and light Fries rearrangement is exaggerated under the effect of heat.But even if side chain type polymeric membrane of the present invention is by heating in the situation that is mesomorphic state, if heating-up temperature is low, the viscosity of the side chain type polymeric membrane of mesomorphic state is high, is difficult to the reorientation by self assembly.For example, heating-up temperature is no more than than in the scope of the temperature of 10 DEG C of the lower limits for height of the liquid crystal temperature range of side chain type polymeric membrane of the present invention in the case of the highest, cannot produce the anisotropic amplification effect being caused by heat in enough side chain type polymeric membranes of the present invention.
In addition,, even if side chain type polymeric membrane of the present invention is mesomorphic state by heating, if heating-up temperature is high, the state of side chain type polymeric membrane, close to isotropic liquid condition, is difficult to by self assembly towards a direction reorientation.For example, heating-up temperature is in the situation with temperature higher compared with the temperature of low 10 DEG C of the upper limit of the liquid crystal temperature range of side chain type polymeric membrane of the present invention, cannot produce the anisotropic amplification effect being caused by heat in enough side chain type polymeric membranes of the present invention.
As mentioned above, in the manufacture method of liquid crystal orientation film of the present invention, in order to introduce anisotropy efficiently in side chain type polymeric membrane, determine suitable heating-up temperature taking the liquid crystal temperature range of this side chain type polymeric membrane as benchmark.And as mentioned above, the temperature of the postradiation heating of polarized UV rays is made as taking than the temperature of 10 DEG C of the lower limits for height of the liquid crystal temperature range of this side chain type polymeric membrane as lower limit, taking the temperature in the scope of the upper limit than the temperature of low 10 DEG C of the upper limit of liquid crystal temperature range.Therefore, for example liquid crystal temperature range of side chain type polymeric membrane of the present invention is that in the situation of 100 DEG C～200 DEG C, the temperature of the postradiation heating of polarized UV rays is preferably 110 DEG C～190 DEG C.By this, can give side chain type polymeric membrane of the present invention with larger anisotropy.
Above the orientation process in the manufacture method of liquid crystal orientation film of the present invention is illustrated, then the manufacture method of liquid crystal orientation film of the present invention is described.
The manufacture method of liquid crystal orientation film of the present invention comprises the operation of following [I]～[III] or the operation of following [I]～[IV] in the following order.Can manufacture and introduce anisotropic liquid crystal orientation film with high-level efficiency.
[I] forms the operation of the photosensitive side chain type polymeric membrane that can embody liquid crystal liquid crystal property on substrate;
[II] irradiates the operation of polarized UV rays to the side chain type polymeric membrane obtaining in operation [I];
[III] operation to the side chain type polymeric membrane heating of irradiating through polarized UV rays in operation [II];
[IV] was to irradiating described ultraviolet ray, then irradiating unpolarized ultraviolet operation through the side chain type polymeric membrane of heating.
Below, each operation of the operation of [I] included to the manufacture method of liquid crystal orientation film of the present invention～[III] or the operation of following [1]～[IV] describes.
In operation [I], on substrate, form side chain type polymeric membrane of the present invention.Substrate is not particularly limited.For example, except glass substrate, can use the transparency carriers such as plastic base such as acrylic acid substrate and polycarbonate substrate.Consider the application of gained liquid crystal orientation film, consider from the viewpoint of the simplification of the manufacturing process of liquid crystal display cells, also can use the substrate of ITO (Indium Tin Oxide: the tin indium oxide) electrode that is formed with liquid crystal drive and uses etc.In addition, consider the application in reflection type liquid crystal display element, also can use the opaque substrates such as silicon wafer, electrode now also can use the catoptrical materials such as aluminium.
Side chain type polymeric membrane of the present invention is in the situation of solution shape that is dissolved in required solvent, and the film on substrate forms and undertaken by the side chain type polymeric membrane That is coated with this solution shape.Coating process is not particularly limited, and industrial circle adopts the method being coated with by serigraphy, hectographic printing, flexographic printing or ink-jet method etc. conventionally.As other coating process, there are dip coating, rolling method, slot coated method, spin-coating method (method of spin coating) or spraying process etc., can use these methods according to object.
On substrate after the side chain type polymeric membrane of the present invention of coating solution shape, can by the heating arrangements such as heating plate, heat-circulation type stove or IR (infrared ray) type stove 20 DEG C～180 DEG C, preferably at 40 DEG C～150 DEG C, make solvent evaporation, thereby obtain side chain type polymeric membrane of the present invention.If the thickness of side chain type polymeric membrane is blocked up, unfavorable aspect the power consumption of liquid crystal display cells that uses liquid crystal orientation film; If cross thinly, the reliability of liquid crystal display cells reduces sometimes, therefore preferably 5nm～300nm, more preferably 10nm～100nm.
In addition, also can be after [I] operation, the operation that the substrate that is formed with side chain type polymeric membrane is cooled to room temperature is set before follow-up [II] operation.
In operation [II], the side chain type polymeric membrane obtaining in operation [I] is irradiated to polarized UV rays.The face of side chain type polymeric membrane is irradiated in the situation of polarized UV rays, across polaroid, substrate is irradiated to polarized UV rays from certain orientation.As ultraviolet ray used, can use the ultraviolet ray in the scope of wavelength 100nm～400nm.Better to select suitable wavelength according to the kind of side chain type polymeric membrane used by wave filter etc.For example, in order optionally to bring out photo-crosslinking, the ultraviolet ray in can the scope of choice for use wavelength 250nm～400nm.As ultraviolet ray, for example, can use the light of being launched by high-pressure sodium lamp.
About the exposure of polarized UV rays, as mentioned above, preferably in 1%～70% scope of the amount of the polarized UV rays that realizes Δ Amax of used side chain type polymeric membrane of the present invention, more preferably in 1%～50% scope.
In operation [III], to the side chain type polymeric membrane heating of irradiating through polarized UV rays in operation [II].Add the heating arrangements such as thermal recovery heating plate, heat-circulation type stove or IR (infrared ray) type stove.About the temperature of heating, as mentioned above, can consider that the temperature that used side chain type polymeric membrane of the present invention embodies liquid crystal liquid crystal property determines., the postradiation heating-up temperature of polarized UV rays is preferably taking the temperature of 10 DEG C of lower limits for height of liquid crystal temperature range that embodies liquid crystal liquid crystal property than the side chain type polymeric membrane of the present invention being used as lower limit, taking the temperature in the scope of the upper limit than the temperature of low 10 DEG C of the upper limit of liquid crystal temperature range.
By comprising above operation, by the manufacture method of liquid crystal orientation film of the present invention, can in side chain type polymeric membrane, introduce anisotropy efficiently.And can manufacture efficiently liquid crystal orientation film of the present invention.
In operation [IV], to irradiating described ultraviolet ray, then irradiating unpolarized ultraviolet ray through the side chain type polymeric membrane of heating.By this operation, unreacted in [II] operation and side chain type polymeric membrane generation cross-linking reaction of the present invention residual, that reorientation occurs in [III] operation, orientation stabilization.
Be better that ultraviolet ray by [IV] operation is irradiated, make 20 % by mole of photocrosslinking reaction group that described side chain type polymeric membrane has to react above.In other words,, if do not have more than 20 % by mole photocrosslinking reaction groups left behind, in this operation, be not easy fully to realize orientation stabilization in [II] operation.Its reason is, the photoreactive group of reorientation is difficult to keep its state of orientation and immobilization.In the situation of above formula (6), (7), if carry out this operation, effect of the present invention is not easy performance on the contrary.
Embodiment
Enumerating embodiment is described in detail embodiments of the present invention.But the present invention should not be construed as limited to this.
< synthesis example 1>
By 4,4 '-'-biphenyl diphenol and 1,6-dibromo-hexane heat under alkali condition, thus synthetic 4 '-(the own oxygen base of 6-bromine) biphenyl-4-phenol.This product is reacted with lithium methacrylate, obtain the own oxygen ylmethyl acrylate of 2-(4 '-xenol-4-base oxygen base).Then, under alkali condition, add 4-methoxyl cinnamoyl chloride, the compound shown in synthetic following formula (9).
< synthesis example 2>
1-hydroxycinnamic acid and 1-hydroxyl-6-hexanol are heated under alkali condition, thus synthetic 4-(the own oxygen base of 6-hydroxyl) cinnamic acid.This product is reacted under alkali condition with methacrylic chloride, obtain the compound shown in following formula (10).
< synthesis example 3>
1-hydroxybenzoic acid and 1-hydroxyl-6-hexanol are heated under alkali condition, thus synthetic 4-(the own oxygen base of 6-hydroxyl) benzoic acid.This product is reacted under alkali condition with methacrylic chloride, obtain the compound shown in following formula (11).
< synthesis example 4>
4-iodophenol and the chloro-1-hexanol of 6-are heated under alkali condition, thus synthetic 4-(the own oxygen base of 6-hydroxyl) iodophenol.After this product is reacted with 2-methyl-3-butyne-2-alcohol, under alkali condition, heat, thereby obtain 4-(the own oxygen base of 6-hydroxyl) ethynylbenzene (compd A).In addition, by other approach, 4-methoxyl cinnamoyl chloride is reacted with 4-iodophenol, synthetic 4-iodophenyl-3-(4-methoxyphenyl) acrylate (compd B).Then, compd A and compd B are reacted under alkali condition, thereby obtain the compound shown in following formula (12).
< synthesis example 5>
1-hydroxybenzoic acid and 1-hydroxyl-6-hexanol are heated under alkali condition, thereby after synthetic 4-(the own oxygen base of 6-hydroxyl) benzoic acid, add thionyl chloride, thereby obtain 4-(the own oxygen base of 6-hydroxyl) chlorobenzoyl chloride.This product is reacted under alkali condition with p methoxy phenol, obtain the compound shown in following formula (13).
< synthesis example 6>
Methacrylate shown in above formula (9) is dissolved in tetrahydrofuran, adds azoisobutyronitrile (AIBN) and carry out polymerization as reaction initiator, thereby obtain polymkeric substance 1.This polymkeric substance 1 demonstrates liquid crystal liquid crystal property in the temperature range of 116 DEG C～315 DEG C.
< synthesis example 7>
Methacrylate shown in above formula (10) is dissolved in tetrahydrofuran, adds azoisobutyronitrile (AIBN) and carry out polymerization as reaction initiator, thereby obtain polymkeric substance 2.This polymkeric substance 2 demonstrates liquid crystal liquid crystal property in the temperature range of 135 DEG C～187 DEG C.
< synthesis example 8>
Methacrylate shown in methacrylate shown in above formula (10) and above formula (11) is dissolved in tetrahydrofuran with 25 to 75 ratio, add azoisobutyronitrile (AIBN) and carry out polymerization as reaction initiator, thereby obtain polymkeric substance 3.This polymkeric substance 3 demonstrates liquid crystal liquid crystal property in the temperature range of 146 DEG C～183 DEG C.
< synthesis example 9>
Methacrylate shown in above formula (12) is dissolved in tetrahydrofuran, adds azoisobutyronitrile (AIBN) and carry out polymerization as reaction initiator, thereby obtain polymkeric substance 4.This polymkeric substance 4 demonstrates liquid crystal liquid crystal property in the temperature range of 66 DEG C～320 DEG C.
< synthesis example 10>
Methacrylate shown in above formula (13) is dissolved in tetrahydrofuran, adds azoisobutyronitrile (AIBN) and carry out polymerization as reaction initiator, thereby obtain polymkeric substance 5.This polymkeric substance 5 demonstrates liquid crystal liquid crystal property in the temperature range of 143 DEG C～283 DEG C.
[changing 4]
< has introduced the preparation > of anisotropic liquid crystal orientation film
< embodiment 1>
Use the polymkeric substance 1 obtaining in synthesis example 6, be dissolved in methylene chloride, be spin-coated on optically isotropic substrate with the thickness of about 190nm, thereby on substrate, form side chain type polymeric membrane.With this basal lamina determination ultra-violet absorption spectrum, result maximum absorbance is 0.89 at 314nm place.Side chain type polymeric membrane on the substrate of gained is irradiated to the ultraviolet ray that converts rectilinearly polarized light by Glan-Taylor prism to.
With the side chain type polymeric membrane mensuration ultra-violet absorption spectrum on the substrate obtaining as mentioned above, evaluate Δ A, what this Δ A was the ultraviolet absorbance of side chain type polymeric membrane, the direction parallel with the polarization direction of the polarized UV rays of irradiating with the ultraviolet absorbance of the direction vertical with the polarization direction of the polarized UV rays of irradiation is poor.Irradiate while being scaled the polarized UV rays of 4500mJ with wavelength 365nm, Δ A is 0.2 to the maximum at 314nm place, irradiate 650mJ polarized UV rays so that Δ A reach 0.065 (with respect to maximal value have 32% poor), then by this base plate heating to 155 DEG C, make side chain type polymeric membrane be liquid crystal phase, keep 5 minutes with this state.Then be cooled to room temperature, obtain having to the substrate of having introduced anisotropic side chain type polymeric membrane in film.Δ A is now amplified to 1.8, and the degree of orientation is 0.73.Then, the substrate of having introduced anisotropic side chain type polymeric membrane to having irradiates and is scaled the unpolarized ultraviolet ray of 1500mJ with wavelength 365nm, thereby obtains having the substrate of liquid crystal orientation film.
< embodiment 2>
The polymkeric substance 1 obtaining in using synthesis example 6, the exposure of polarized UV rays, for 500mJ (Δ A reaches the exposure of Δ A peaked 25%), are carried out polarized UV rays irradiation and thermal treatment subsequently similarly to Example 1.Consequently, the Δ A before and after thermal treatment is amplified to 1.85 from 0.05, and the degree of orientation is now 0.74 at 314nm place.Then irradiate similarly to Example 1 unpolarized ultraviolet ray, obtain having the substrate of liquid crystal orientation film.
< embodiment 3>
Except the polymkeric substance obtaining in synthesis example 72 is dissolved in tetrahydrofuran, taking the thickness of about 150nm be spin-coated on optically isotropic substrate, the exposure of polarized UV rays is as 5mJ (Δ A reaches the exposure of Δ A peaked 10%), thermal treatment are subsequently at 165 DEG C 5 minutes, carries out similarly to Example 1 that polarized UV rays is irradiated and thermal treatment subsequently.Consequently, the Δ A before and after thermal treatment is amplified to 1.6 from 0.03, and the degree of orientation is now 0.72 at 314nm place.Then irradiate similarly to Example 1 the unpolarized ultraviolet ray of 1000mJ, obtain having the substrate of liquid crystal orientation film.
< embodiment 4>
The polymkeric substance 3 obtaining in using synthesis example 8, the exposure of polarized UV rays, for 20mJ (Δ A reaches the exposure of Δ A peaked 40%), are carried out polarized UV rays irradiation and thermal treatment subsequently similarly to Example 3.Consequently, the Δ A before and after thermal treatment is amplified to 1.6 from 0.12, and the degree of orientation is now 0.62 at 314nm place.Then irradiate similarly to Example 1 the unpolarized ultraviolet ray of 1000mJ, obtain having the substrate of liquid crystal orientation film.
< embodiment 5>
Except the polymkeric substance obtaining in synthesis example 94 is dissolved in methylene chloride, taking the thickness of about 220nm be spin-coated on optically isotropic substrate and the exposure that forms side chain type polymeric membrane, polarized UV rays on substrate as 300mJ (Δ A reaches the exposure of Δ A peaked 29%), thermal treatment are subsequently at 200 DEG C 5 minutes, carry out similarly to Example 1 that polarized UV rays is irradiated and thermal treatment subsequently.Consequently, the Δ A before and after thermal treatment is amplified to 1.4 from 0.04, and the degree of orientation is now 0.62 at 294nm place.Then irradiate similarly to Example 1 the unpolarized ultraviolet ray of 5000mJ, obtain having the substrate of liquid crystal orientation film.
< embodiment 6>
Except the polymkeric substance obtaining in synthesis example 10 5 is dissolved in methylene chloride, taking the thickness of about 220nm be spin-coated on optically isotropic substrate and the exposure that forms side chain type polymeric membrane, polarized UV rays on substrate as 1000mJ (Δ A reaches the exposure of Δ A peaked 49%), thermal treatment are subsequently at 180 DEG C 5 minutes, carry out similarly to Example 1 that polarized UV rays is irradiated and thermal treatment subsequently.Consequently, obtain having the substrate of the liquid crystal orientation film that Δ A before and after the thermal treatment degree of orientation from 0.07 being amplified to 1.7, is now 0.72 at 262nm.
< comparative example 1>
Use the polymkeric substance 1 obtaining in synthesis example 6, be dissolved in methylene chloride, be spin-coated on optically isotropic substrate and on substrate, form side chain type polymeric membrane with the thickness of about 190nm.With this basal lamina determination ultra-violet absorption spectrum, result maximum absorbance is 0.89 at 314nm place.Side chain type polymeric membrane on the substrate of gained is irradiated to the ultraviolet ray that converts rectilinearly polarized light by Glan-Taylor prism to.
With the side chain type polymeric membrane mensuration ultra-violet absorption spectrum on the substrate obtaining as mentioned above, evaluate Δ A, what this Δ A was the ultraviolet absorbance of side chain type polymeric membrane, the direction parallel with the polarization direction of the polarized UV rays of irradiating with the ultraviolet absorbance of the direction vertical with the polarization direction of the polarized UV rays of irradiation is poor.Irradiate while being scaled the polarized UV rays of 4500mJ with wavelength 365nm, Δ A is 0.2 to the maximum at 314nm place, irradiate 650mJ polarized UV rays so that Δ A reach 0.065 (with respect to maximal value have 32% poor), then by this base plate heating to 155 DEG C, make side chain type polymeric membrane be liquid crystal phase, keep 5 minutes with this state.Then be cooled to room temperature, obtain having to the substrate of having introduced anisotropic liquid crystal orientation film in film.Δ A is now amplified to 1.8, and the degree of orientation is 0.73.
< comparative example 2>
Except the polymkeric substance obtaining in synthesis example 61 is dissolved in methylene chloride, taking the thickness of about 190nm be spin-coated on optically isotropic substrate and the exposure that forms side chain type polymeric membrane, polarized UV rays on substrate as 4500mJ (Δ A reaches peaked exposure), similarly carry out polarized UV rays irradiation and thermal treatment subsequently with comparative example 1, obtain having introduced anisotropic liquid crystal orientation film in film.Now, the Δ A before and after thermal treatment does not change, and is still 0.07, and the degree of orientation is also 0.12 at 314nm place, the amplification to Δ A and the degree of orientation unconfirmed.
< comparative example 3>
Except the polymkeric substance obtaining in synthesis example 72 is dissolved in tetrahydrofuran, taking the thickness of about 150nm be spin-coated on optically isotropic substrate and the exposure that forms side chain type polymeric membrane, polarized UV rays on substrate as 900mJ (Δ A reaches peaked exposure), thermal treatment are subsequently as 165 DEG C, similarly carry out polarized UV rays irradiation and thermal treatment subsequently with comparative example 1, obtain having introduced anisotropic liquid crystal orientation film in film.Now, the Δ A before and after thermal treatment does not change, and is still 0.07, and the degree of orientation is also 0.12 at 314nm place, the amplification to Δ A and the degree of orientation unconfirmed.
< comparative example 4>
Except the polymkeric substance obtaining in synthesis example 72 is dissolved in tetrahydrofuran, taking the thickness of about 150nm be spin-coated on optically isotropic substrate and the exposure that forms side chain type polymeric membrane, polarized UV rays on substrate as 5mJ (Δ A reaches the exposure of Δ A peaked 10%), thermal treatment subsequently as 200 DEG C, more than the liquid crystal temperature range of polymkeric substance 2, similarly carry out polarized UV rays irradiation and thermal treatment subsequently with comparative example 1, obtain liquid crystal orientation film.Now, the Δ A before and after thermal treatment reduces to 0 from 0.07, and orientation is also 0 at 314nm place, the anisotropy disappearance in macromolecule membrane.
The preparation of < liquid crystal structure cell and evaluation >
< embodiment 7>
With the substrate with liquid crystal orientation film of making in two embodiment 1, the liquid crystal ZLI-4792 of Merck Amada Co., Ltd. (メ Le Network ジ ャ パ Application) system is clamped, obtain antiparallel type liquid crystal structure cell.Under cross Nicols, observe gained liquid crystal structure cell, result is observed the uniform liquid crystal aligning bad without orientation.In addition, make two and introduced the ito substrate of anisotropic liquid crystal orientation film with this, liquid crystal ZLI-4792 is clipped between them, by pair of straight linear polarizer, gained liquid crystal structure cell is clamped again, thereby the thickness of making liquid crystal is TN (Twisted Nematic: twisted-nematic) the type liquid crystal display cells of 6 μ m.In this TN type liquid crystal display cells, by ITO electrode application voltage, can confirm the driving of liquid crystal.Confirm that liquid crystal display cells is not all orientated defect on whole, confirm the change in orientation of uniform liquid crystal by applying voltage.Use the liquid crystal orientation film of present embodiment, can be made into the liquid crystal display cells of present embodiment.Evaluation result is summarized in table 1.
< embodiment 8>
Use the substrate with liquid crystal orientation film of making in two embodiment 2, make liquid crystal structure cell by method similarly to Example 7.The results are shown in table 1.
< embodiment 9>
Use the substrate with liquid crystal orientation film of making in two embodiment 3, make liquid crystal structure cell by method similarly to Example 7.The results are shown in table 1.
< embodiment 10>
Use the substrate with liquid crystal orientation film of making in two embodiment 4, make liquid crystal structure cell by method similarly to Example 7.The results are shown in table 1.
< embodiment 11>
Use the substrate with liquid crystal orientation film of making in two embodiment 5, make liquid crystal structure cell by method similarly to Example 7.The results are shown in table 1.
< embodiment 12>
Use the substrate with liquid crystal orientation film of making in two embodiment 6, make liquid crystal structure cell by method similarly to Example 7.The results are shown in table 1.
< comparative example 5>
Use the substrate with liquid crystal orientation film of making in two comparative examples 1, make liquid crystal structure cell by method similarly to Example 7.The results are shown in table 1.
< comparative example 6>
Use the substrate with liquid crystal orientation film of making in two comparative examples 2, make liquid crystal structure cell by method similarly to Example 7.The results are shown in table 1.
< comparative example 7>
Use the substrate with liquid crystal orientation film of making in two comparative examples 3, make liquid crystal structure cell by method similarly to Example 7.The results are shown in table 1.
< comparative example 8>
Use the substrate with liquid crystal orientation film of making in two comparative examples 4, make liquid crystal structure cell by method similarly to Example 7.The results are shown in table 1.
From above evaluation result, the liquid crystal orientation film of the present invention that adopt the manufacture method of liquid crystal orientation film of the present invention, makes with less ultraviolet irradiation amount can provide liquid crystal display cells.
[table 1]
| Embodiment and comparative example | The orientation of liquid crystal |
| Embodiment 7 | Well |
| Embodiment 8 | Well |
| Embodiment 9 | Well |
| Embodiment 10 | Well |
| Embodiment 11 | Well |
| Embodiment 12 | Well |
| Comparative example 5 | A large amount of orientation defects |
| Comparative example 6 | Without orientation |
| Comparative example 7 | Without orientation |
| Comparative example 8 | Without orientation |
The possibility of utilizing in industry
Manufacture method of the present invention can be used for the manufacture of the liquid crystal orientation film that can realize high efficiency orientation process.
In addition, all the elements of instructions, claims, accompanying drawing and summary of quoting No. 2011-260180, the Japanese patent application of filing an application November 29 in 2011 are here as the announcement of instructions of the present invention.
The explanation of symbol
1 side chain type polymeric membrane
2,2a side chain
3 side chain type polymeric membranes
4,4a side chain
5 side chain type polymeric membranes
6,6a side chain
7 side chain type polymeric membranes
8,8a side chain
Claims (12)
1. a manufacture method for liquid crystal orientation film, it comprises:
[I] is formed on the operation that embodies the photosensitive side chain type polymeric membrane of liquid crystal liquid crystal property in the temperature range of regulation on substrate;
[II] irradiates the operation of polarized UV rays to described side chain type polymeric membrane; And
[III] operation to the side chain type polymeric membrane heating of irradiating through described ultraviolet ray;
It is characterized in that, the ultraviolet irradiation amount of [II] operation is in Δ A reaches 1%～70% scope of maximum ultraviolet irradiation amount, and Δ A is the poor of the ultraviolet absorbance of described side chain type polymeric membrane, the direction parallel with the polarization direction of described polarized UV rays and the ultraviolet absorbance of the direction vertical with the polarization direction of described polarized UV rays.
2. the manufacture method of liquid crystal orientation film as claimed in claim 1, is characterized in that, the ultraviolet irradiation amount of [II] operation is in described Δ A reaches 1%～50% scope of maximum ultraviolet irradiation amount.
3. the manufacture method of liquid crystal orientation film as claimed in claim 1 or 2, it is characterized in that, the heating-up temperature of [III] operation is to embody the temperature of 10 DEG C of the lower limits for height of the temperature range of liquid crystal liquid crystal property～than the temperature in the scope of the temperature of low 10 DEG C of the upper limit of this temperature range than described side chain type polymeric membrane.
4. the manufacture method of the liquid crystal orientation film as described in any one in claim 1～3, it is characterized in that, described in to embody contained photonasty group in the photosensitive side chain type macromolecule of liquid crystal liquid crystal property be azobenzene, Stilbene, cinnamic acid, cinnamate, chalcone, cumarin, tolane, phenol benzoate or derivatives thereof.
5. a manufacture method for liquid crystal orientation film, it comprises:
[I] is formed on the operation that embodies the side chain type polymeric membrane of the photocrosslinking reaction of liquid crystal liquid crystal property in the temperature range of regulation on substrate;
[II] irradiates the operation of polarized UV rays to described photocrosslinking reaction side chain type polymeric membrane; And
[III] operation to the side chain type polymeric membrane heating of irradiating through described ultraviolet ray;
[IV] was to irradiating described ultraviolet ray, then irradiating unpolarized ultraviolet operation through the side chain type polymeric membrane of heating;
It is characterized in that, the ultraviolet irradiation amount of [II] operation is in Δ A reaches 1%～70% scope of maximum ultraviolet irradiation amount, and Δ A is the poor of the ultraviolet absorbance of described side chain type polymeric membrane, the direction parallel with the polarization direction of described polarized UV rays and the ultraviolet absorbance of the direction vertical with the polarization direction of described polarized UV rays.
6. the manufacture method of liquid crystal orientation film as claimed in claim 5, is characterized in that, the ultraviolet irradiation amount of [II] operation is in described Δ A reaches 1%～50% scope of maximum ultraviolet irradiation amount.
7. the manufacture method of the liquid crystal orientation film as described in claim 5 or 6, it is characterized in that, the heating-up temperature of [III] operation is to embody the temperature of 10 DEG C of the lower limits for height of the temperature range of liquid crystal liquid crystal property～than the temperature in the scope of the temperature of low 10 DEG C of the upper limit of this temperature range than described side chain type polymeric membrane.
8. the manufacture method of the liquid crystal orientation film as described in any one in claim 5～7, is characterized in that, irradiates by the ultraviolet ray of [IV] operation, and 20 % by mole of the photocrosslinking reaction group that described side chain type polymeric membrane has react above.
9. the manufacture method of the liquid crystal orientation film as described in any one in claim 5～8, it is characterized in that, described in to embody contained photonasty group in the side chain type macromolecule of photocrosslinking reaction of liquid crystal liquid crystal property be cinnamic acid, cinnamate, chalcone, cumarin, tolane or derivatives thereof.
10. the manufacture method of the liquid crystal orientation film as described in any one in claim 1～9, it is characterized in that, described side chain type polymeric membrane is the structure that comprises main chain and side chain, described main chain is made up of at least one that is selected from hydrocarbon, acrylate and methacrylate, and described side chain represents with at least one in following formula (1)～(7);
[changing 1]
In formula (1), A
1, B
1represent independently respectively singly-bound ,-O-,-CH
2-,-COO-,-OCO-,-CONH-or NH-CO-, Y
1be at least one group that is selected from the cyclic hydrocarbon of phenyl ring, naphthalene nucleus, cyclohexyl biphenyl, furan nucleus, pyrrole ring and carbon number 5～8, on these groups, the hydrogen atom of bonding can be distinguished independently by-NO
2,-CN ,-C=C (CN)
2,-C=CH-CN, halogen group, alkyl or alkoxy replace; X
1represent singly-bound ,-COO-,-OCO-,-N=N-,-C=C-,-C ≡ C-or C
6h
4-, l1 represents 1～12 integer, and m1 represents 1～3 integer, and n1 represents 1～12 integer; In formula (2), A
2, B
2, D
1represent independently respectively singly-bound ,-O-,-CH
2-,-COO-,-OCO-,-CONH-or NH-CO-, Y
2be at least one group that is selected from the cyclic hydrocarbon of phenyl ring, naphthalene nucleus, cyclohexyl biphenyl, furan nucleus, pyrrole ring and carbon number 5～8, on these groups, the hydrogen atom of bonding can be distinguished independently by-NO
2,-CN ,-C=C (CN)
2,-C=CH-CN, halogen group, alkyl or alkoxy replace; X
2represent singly-bound ,-COO-,-OCO-,-N=N-,-C=C-,-C ≡ C-or C
6h
4-, R
1represent the alkyl of hydrogen atom or carbon number 1～6; L2 represents 1～12 integer, and m2 represents 1～3 integer, and n2 represents 1～12 integer; In formula (3), A
3represent singly-bound ,-O-,-CH
2-,-COO-,-OCO-,-CONH-or NH-CO-, X
3represent singly-bound ,-COO-,-OCO-,-N=N-,-C=C-,-C ≡ C-or C
6h
4-, R
2represent the alkyl of hydrogen atom or carbon number 1～6; L3 represents 1～12 integer, and m3 represents 1～3 integer; In formula (4), l4 represents 1～12 integer; In formula (5), A
4represent singly-bound ,-O-,-CH
2-,-COO-,-OCO-,-CONH-or NH-CO-, X
4expression-COO-, Y
3be at least one group that is selected from phenyl ring, naphthalene nucleus and cyclohexyl biphenyl, on these groups, the hydrogen atom of bonding can be distinguished independently by-NO
2,-CN ,-C=C (CN)
2,-C=CH-CN, halogen group, alkyl or alkoxy replace; L5 represents 1～12 integer, and m4 represents 1～3 integer; In formula (6), A
5represent singly-bound ,-O-,-CH
2-,-COO-,-OCO-,-CONH-or NH-CO-, R
3represent to be selected from hydrogen atom ,-NO
2,-CN ,-C=C (CN)
2at least one group of the alkyl of ,-C=CH-CN, halogen group, carbon number 1～6 and the alkoxy of carbon number 1～6; L6 represents 1～12 integer; On phenyl ring in formula (6), the hydrogen atom of bonding can be distinguished independently by-NO
2,-CN ,-C=C (CN)
2,-C=CH-CN, halogen group, alkyl or alkoxy replace; In formula (7), A
6represent singly-bound ,-O-,-CH
2-,-COO-,-OCO-,-CONH-or NH-CO-, B
3represent singly-bound ,-COO-,-OCO-,-N=N-,-C=C-,-C ≡ C-or C
6h
4-; W
1be at least one group that is selected from the cyclic hydrocarbon of phenyl ring, naphthalene nucleus, cyclohexyl biphenyl, furan nucleus, pyrrole ring and carbon number 5～8, on these groups, the hydrogen atom of bonding can be distinguished independently by-NO
2,-CN ,-C=C (CN)
2,-C=CH-CN, halogen group, alkyl or alkoxy replace; L7 represents 1～12 integer, and m5, m6 represent respectively 1～3 integer.
11. 1 kinds of liquid crystal orientation films, is characterized in that, make by the manufacture method of the liquid crystal orientation film described in any one in claim 1～10.
12. 1 kinds of liquid crystal display cells, is characterized in that, have the liquid crystal orientation film described in claim 11.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2011260180 | 2011-11-29 | ||
| JP2011-260180 | 2011-11-29 | ||
| PCT/JP2012/080977 WO2013081066A1 (en) | 2011-11-29 | 2012-11-29 | Method for manufacturing liquid crystal alignment film, liquid crystal alignment film, and liquid crystal display element |
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| Publication Number | Publication Date |
|---|---|
| CN103959152A true CN103959152A (en) | 2014-07-30 |
| CN103959152B CN103959152B (en) | 2016-11-30 |
Family
ID=
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Also Published As
| Publication number | Publication date |
|---|---|
| JP2017090934A (en) | 2017-05-25 |
| TWI593710B (en) | 2017-08-01 |
| KR102012533B1 (en) | 2019-08-20 |
| JPWO2013081066A1 (en) | 2015-04-27 |
| JP6150731B2 (en) | 2017-06-21 |
| KR20190099085A (en) | 2019-08-23 |
| WO2013081066A1 (en) | 2013-06-06 |
| TW201341413A (en) | 2013-10-16 |
| KR20140105446A (en) | 2014-09-01 |
| KR102157012B1 (en) | 2020-09-16 |
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